Compositions and methods for visible-light-controlled ruthenium-catalyzed olefin metathesis

Abstract

The present disclosure provides compositions and methods for metathesizing a first alkenyl or alkynyl group with a second alkenyl or alkynyl group, the composition comprising a ruthenium metathesis catalyst and a photoredox catalyst that is activated by visible light.

What is claimed is: 
     
       1. A composition for metathesizing a first alkenyl or alkynyl group with a second alkenyl or alkynyl group, the composition comprising: a ruthenium metathesis catalyst of Formula (I): 
       
         
           
           
               
               
           
         
       
       wherein:
 R 1  is H, C 1-6 alkyl, C 2-6 alkenyl, aryl, or heteroaryl; 
 R 2  to R 5  are, independently in each occurrence, H, C 1-6 alkyl, C 1-6 alkoxy, halo, or aryl; and 
 w to z are, independently, 0 to 5; 
 and a photoredox catalyst that is activated by visible light that is of Formula (A): 
 
       
         
           
           
               
               
           
         
       
       wherein:
 R 6 , R 7 , and R 8  are, independently in each occurrence, H, halo, optionally substituted C 1-6 alkyl, optionally substituted C 1-6 alkoxy, optionally substituted C 1-6 haloalkyl, CN, NO 2 , optionally substituted aryl, optionally substituted heteroaryl, optionally substituted vinyl, C(O)OR L , CON(R L ) 2 , or C(O)R L , where R L  is H, optionally substituted C 1-6 alkyl, C 1-6 heteroalkyl, C 3-8 cycloalkyl, aryl, or heteroaryl; 
 m, n, and p are, independently, 0 to 5; 
 X is O or S; and 
 Y is BF 4 , PF 6 , SbF 6 , B(optionally substituted aryl) 4 , ClO 4   − , halo, or an anion where the conjugate acid has a pKa lower than 4.5. 
 
     
     
       2. The composition of  claim 1 , wherein the visible light has a wavelength of about 350 nm to about 750 nm. 
     
     
       3. The composition of  claim 1 , wherein the ruthenium catalyst is 
       
         
           
           
               
               
           
         
       
     
     
       4. The composition of  claim 1 , wherein the ruthenium metathesis complex is (IMes) 2 RuCl 2 CHPh. 
     
     
       5. The composition of  claim 1 , wherein the photoredox catalyst is: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       6. The composition of  claim 1 , wherein the photocatalyst is 2,4,6-triphenylpyrylium tetrafluoroborate (TPPT): 
       
         
           
           
               
               
           
         
       
     
     
       7. A method for chemical metathesis, comprising applying visible light to (i) one compound comprising a first alkenyl or alkynyl group and a second alkenyl or alkynyl group or (ii) a first compound comprising a first alkenyl or alkynyl group and a second compound comprising a second alkenyl or alkynyl group, in the presence of the composition of  claim 1 . 
     
     
       8. The method of  claim 7 , wherein the visible light has a wavelength of about 350 nm to about 750 nm. 
     
     
       9. The method of  claim 7 , wherein the ruthenium catalyst is 
       
         
           
           
               
               
           
         
       
     
     
       10. The method of  claim 7 , wherein the ruthenium metathesis complex is (IMes) 2 RuCl 2 CHPh. 
     
     
       11. The method of  claim 7 , wherein the photoredox catalyst is: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       12. The method of  claim 7 , wherein the photocatalyst is 2,4,6-triphenylpyrylium tetrafluoroborate (TPPT): 
       
         
           
           
               
               
           
         
       
     
     
       13. The method of  claim 7 , that is performed at a temperature of about 20 to about 30° C. 
     
     
       14. The method of  claim 7 , comprising about 0.01 to about 10 mol %, based on the mol % of the one compound or first and second compound, of the ruthenium metathesis catalyst. 
     
     
       15. The method of  claim 7 , wherein the concentration of the one compound or first and second compound is about 0.01 to about 5 M. 
     
     
       16. A method of spatially controlling a metathesis, comprising:
 forming a mixture of the composition of  claim 1  and one or more compounds susceptible to metathesis; and 
 applying visible light to one or more regions of the mixture so as to give rise to one or more metathesized regions and one or more unmetathesized regions. 
 
     
     
       17. The method of  claim 16 , wherein the visible light is applied using a high resolution light source. 
     
     
       18. The method of  claim 16 , wherein at least one of the unmetathesized regions is covered with a photomask. 
     
     
       19. The method of  claim 16 , wherein the mixture is disposed on a substrate that is functionalized with the one or more compounds susceptible to metathesis. 
     
     
       20. A method of spatially controlling a metathesis, comprising:
 applying visible light to the composition of  claim 1  and one or more compounds susceptible to metathesis, the applying being performed so as to give rise to one or more metathesized regions, 
 at least one of the ruthenium metathesis catalyst and the photoredox catalyst being linked to a substrate, the substrate optionally being stationary. 
 
     
     
       21. The method of  claim 20 , wherein the visible light is applied in a predetermined pattern.